Effects of LaFeO3 Morphology on Oxygen Species and Chemical Looping Partial Oxidation of Methane

IF 7.2 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Chemistry of Materials Pub Date : 2025-04-04 DOI:10.1021/acs.chemmater.5c0028710.1021/acs.chemmater.5c00287

Henglong Li, Pengheng Li, Min Lin and Xing Zhu*,

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Abstract

The design of oxygen carriers is essential for the chemical looping partial oxidation of methane (CL-POM) in syngas production. LaFeO₃ is a promising oxygen storage material, but the impact of its morphology on the reaction characteristics and mechanisms in CL-POM remains unclear. Herein, we synthesized and characterized LaFeO₃ samples with diverse morphologies (cube, porous microsphere, irregular nanoparticle, and polyhedron) to explore how morphology governs crystal plane exposure, oxygen vacancy formation, and oxygen migration. Results showed that cubic LaFeO₃ not only achieved outstanding oxygen storage capacity (4.18 mmol/g), 2.5 times that of the other three samples combined (1.64 mmol/g), but also demonstrated superior methane reactivity with good low-temperature activity (initial reaction temperature of 500 °C) and the highest methane conversion (78.26% at 750 °C). This impressive performance is due to the synergy between oxygen vacancies and the (110) crystal plane, which optimizes oxygen release and enhances methane adsorption and dissociation. DFT calculations further confirmed that the (110) plane has lower energy barriers for reaction processes than the (100) plane, and more oxygen vacancies enhance reactivity and oxygen migration. This work underscores the pivotal role of LaFeO₃ morphology in advancing the design of oxygen storage materials and a redox catalyst.

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LaFeO3形态对甲烷氧形态及化学环部分氧化的影响

氧载体的设计是合成气生产中甲烷化学环部分氧化（CL-POM）的关键。LaFeO3是一种很有前途的储氧材料，但其形态对CL-POM反应特性和机理的影响尚不清楚。在此，我们合成并表征了不同形貌（立方体、多孔微球、不规则纳米颗粒和多面体）的LaFeO3样品，以探索形貌如何影响晶面暴露、氧空位形成和氧迁移。结果表明，立方LaFeO3不仅具有出色的储氧能力（4.18 mmol/g），是其他3种样品（1.64 mmol/g）的2.5倍，而且具有优异的甲烷反应活性，低温活性良好（反应起始温度为500℃），750℃时甲烷转化率最高（78.26%）。这种令人印象深刻的性能是由于氧空位和（110）晶体平面之间的协同作用，从而优化了氧气释放并增强了甲烷的吸附和解离。DFT计算进一步证实了（110）平面比（100）平面具有更低的反应能垒，更多的氧空位增强了反应活性和氧迁移。这项工作强调了LaFeO3形态在推进储氧材料和氧化还原催化剂设计中的关键作用。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Chemistry of Materials 工程技术-材料科学：综合

CiteScore

14.10

自引率

5.80%

发文量

929

审稿时长

1.5 months

期刊介绍： The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.